Giesbertz K J H, Gritsenko O V, Baerends E J
Section Theoretical Chemistry, VU University, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
J Chem Phys. 2014 May 14;140(18):18A517. doi: 10.1063/1.4867000.
Recently, we have demonstrated that the problems finding a suitable adiabatic approximation in time-dependent one-body reduced density matrix functional theory can be remedied by introducing an additional degree of freedom to describe the system: the phase of the natural orbitals [K. J. H. Giesbertz, O. V. Gritsenko, and E. J. Baerends, Phys. Rev. Lett. 105, 013002 (2010); K. J. H. Giesbertz, O. V. Gritsenko, and E. J. Baerends, J. Chem. Phys. 133, 174119 (2010)]. In this article we will show in detail how the frequency-dependent response equations give the proper static limit (ω → 0), including the perturbation in the chemical potential, which is required in static response theory to ensure the correct number of particles. Additionally we show results for the polarizability for H2 and compare the performance of two different two-electron functionals: the phase-including Löwdin-Shull functional and the density matrix form of the Löwdin-Shull functional.
最近，我们已经证明，在含时单粒子约化密度矩阵泛函理论中寻找合适的绝热近似时出现的问题，可以通过引入一个额外的自由度来描述系统加以解决：自然轨道的相位[K. J. H. 吉斯贝茨、O. V. 格里琴科和E. J. 贝伦兹，《物理评论快报》105, 013002 (2010); K. J. H. 吉斯贝茨、O. V. 格里琴科和E. J. 贝伦兹，《化学物理杂志》133, 174119 (2010)]。在本文中，我们将详细展示频率相关的响应方程如何给出恰当的静态极限(ω → 0)，包括化学势中的微扰，这是静态响应理论中确保正确粒子数所必需的。此外，我们展示了H₂的极化率结果，并比较了两种不同的双电子泛函的性能：包含相位的勒维丁 - 舒尔泛函和勒维丁 - 舒尔泛函的密度矩阵形式。
